DE2638233C2 - Substituted benzoyl ureidodiphenyl ethers, process for their preparation and their use as insecticides - Google Patents

Description

OD

with benzoyl isocyanates of the general formula IU / 7 \ - CO — NCO

(EGG)

or

b) 4-isocyanato-diphenyl ethers of the general formula IV R ²

OCN

(IV)

with benzamides of the general formula V

(V)

in which

R ¹ , R ² , R ³ and η have the meanings given, if appropriate reacted in the presence of a diluent.

3. Use of the substituted bcnzoyl-urcidodiphenylathcr according to Claim 1 for combating Insects.

The present invention relates to substituted benzoyl ureidodiphenyl ethers, several processes for their Manufacture and their use as insecticides.

It is already known that certain Bcn / .oylhurnstoifc. / .. B. 1- [4-chloro- or 3,4-dichlorophenyl] -3- [2,6-dichlorobenzoyl] urine. insecticidal properties bcsit / .cn (compare DE-OS 21 23 236).

It has now been found that the substituted benzoylurcidodiphenyl ethers of the general formula

CO — NH — CO — NH- <f

CN

in which

R ¹ for halogen or Cr to Q-alkyl, io

R ^{2 stands} for chlorine, bromine or hydrogen, R ³ for bromine or hydrogen, and η stands for a whole number from 1 to 3, have strong insecticidal properties.

It has also been found that the substituted benzoylurcidodiphenyl ethers of the general formula (I) 15 can be obtained if one in each case in a manner known per se

a) Phenoxyanilines of the general formula (II) R ²

H ₂ N

• V

CN

(Π)

R ³

with benzoyl isocyanates of the general formula (III) Ri

b) 4-isocyanato-diphenyl ether of the general formula (IV) R ²

(ΠΙ)

OCN

CN

(IV)

with benzamides of the general formula (V)> —NH ₂

(V)

in which

R ¹ , R ² , R ¹ and η have the meanings given, if appropriate in the presence of a diluent

implements.

Surprisingly, the substituted Bcn / .oyl-ureidodiphcnylälher according to the invention have an essential better insecticidal action than the benzoylureas known from the prior art analogous constitution and the same direction of action. The substances that are found to be suitable represent a real one Enrichment of technology.

If, according to process a), 4- (4-cyanophenoxy) -3-bromo-5-chloroaniline and 2-ethylbenzoyl isocyanate are used and according to process b) 4- (4-cyanophenoxy) -3,5-dibromophynyl isocyanate and 2-ethylbenzamide as starting materials, the course of the reaction can be represented by the following formula scheme:

V-CO —NCO + H ₂ N-Hf \ —G— <f V-CN

"<F Λ — CO — NH-CO — NH- ^ f" V-O

b) <f V-CO-NH ₂ + OCN

CO-NH-CO->! H-nf

CN

CN

The starting materials to be used are defined by the general formulas (II) to (V). It says

R ^{1 represents} fluorine, chlorine, bromine, iodine or straight or branched alkyl with 1 to 4, in particular 1 or 2 carbon atoms.

As starting materials to be used Phenoxyaniline (II) can be prepared by methods known from the literature [see Liebigs Annalen 740, pages 169-179 (1970)] or by z. B. 4-chloro-benzonitrile reacts with 4-aminophenolates or by reacting 4-cyanophenolates with 1 -chloro-4-nitro-benzoI derivatives to the corresponding nitro compound, which is then converted into the amino group by reduction, from which by reaction with phosgene the corresponding 4-isocyanatodiphenyl ethers (IV) are obtained.

As examples of the phenoxyanilines (II) and the 4-isocyanato-diphenyl ethers (IV) are mentioned in detail:

3,5-dibromo, 3-chloro, 3-bromo and 3-bromo-5-chloro-4- (4-cyanophenoxy) -aniline, 4- (4-cyanoplienoxy) -aniline and the corresponding isocyanate compounds.

The benzoyl isocyanates (III) also to be used as starting materials are known and can be prepared by generally customary processes [compare AJ Spezial et al. J. Org. Chem. 30 (12), pages 4306-4307 (1965)].

The following are examples of this:

2-fluoro-. 2-chlorine, 2-bromine, 2-iodine, 2-methyl, 2-ethyl, 2,6-difluoro, 2,6-dichloro, 2, 6-dibromo and 2,6 Diiodo benzoyl isocyanate.

The benzamides (V), which are also known and gradually, are also required as starting materials generally customary methods can be produced [compare Beilstein's "Handbuch der Organic Chemistry" Vol. 9, page 336].

The following are examples of this:

2-fluoro, 2-chloro, 2-bromo, 2- | od-, 2-methyl, 2-ethyl, 2,6-difluoro, 2,6-dichloro, 2,6-dibromo - i; nd 2,6-diiodobenzamide.

The processes for preparing the compounds of the invention are preferably used suitable solvents or diluents carried out. As such, practically all inert ones come organic so'ventien in question. These include, in particular, aliphatic and aromatic, if appropriate chlorinated hydrocarbons such as benzene. Toluene, xylene. Bcn / .in, methylene chloride, chloroform, carbon tetrachloride

fuel, chlorobenzene, or ether, ζ. B. Diälhyl- and Dibutylüthcr, dioxane, also ketones, such as acetone. Methyl ethyl, methyl isopropyl and methyl isobutyl ketone, as well as nitriles such as accto- and propionitrile.

The reaction temperature can be varied within a relatively wide range. Generally works between 0 and 120 ° C, preferably at 40 to 80 ° C.

The reaction is generally allowed to proceed under normal pressure. ο

To carry out the process, the starting components are usually used in an equivalent ratio. An excess of one or the other reaction component has no significant advantages. The reaction components are usually combined and mostly in one of the solvents listed above stirred at elevated temperature to complete the reaction for one or more hours and that separating product isolated by suction, washing, drying and possibly recrystallization. the Compounds occur in crystalline form and are characterized by their melting point.

The active ingredients are suitable for combating when the plants are well tolerated and the toxicity to warm-blooded animals is favorable of animal pests, especially insects,

in agriculture, in forests, in stored goods and material protection as well as in the hygiene and veterinary sector occurrence. They are against normally sensitive and rcsistenie species as well as against all or individual develop- ments stages effective. The pests mentioned above include:

From the order of the Isopoda, for. B. Oniscus asellus, Armadillidium vulgar. Porcellio scaber.

From the order of the Diplopoda, for. B. Blaniulus guttulalus.

From the order of the Chilopoda, for. B. Geophilus carpophagus, Scutigera spec.

From the order of the Symphyla z. B. Scutigerclla immaculata.

From the order of the Thysanura, e.g. B. Lepisma saccarina.

From the order of the Collembola, for. B. Onychiurus armatus.

From the order of the Orthoptera, e.g. Blatta oricntalis, Periphlancta americana. Leucophaea maderae, Blattella germanica, Acheta domcsticus, Gryllotalpa spp .. l.ncusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.

From the order of the Dermaptera, for. B. Forficula auricularia.

From the order of the Isoptera, for. B. Retieulitermes spp.

From the order of the Anoplura, e.g. B. Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis.

Haematopinus spp., Linognathus, spp.

From the order of the Mallophaga z. B. Trichodectes spp., Damalinea spp.

From the order of the Thysanoptera z. B. Hercinothrips femoralis. Thrips tabaci.

From the order of the Heteroptera, for. B. Eurygaster spp., Dysdercus intermedius, Piesma quadrata. Cimex lectularius, Rhodnius prolixus, Triatoma spp.

From the order of the Homoptcra, e.g. B. Aleurodes brassicac, umisia tabaci. Trialeurodes vaporariorum. js Aphis gossypii, Brcvicorync brassicac, Cryptomyzus ribi.s, Doralis fabae, Doralis pomi. Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Eusceiis biiobatus, Nephotettix cincticcps, I.ccanium corni, Saissctia olcae. Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp.

From the order of the Lepidoptera, for. B. Pectinophora gossypiclla. Bupalus piniarius, Chematobia brumata.

Lithocolletis blancardella, Hyponomeuta padclla, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp, Bucculatrix thurbcriella, Phyllocnisiis citrella, Agrotis spp., Euxoa spp, Feltia spp., Earias insulana, Heliothis spp .. Laphygma exigua. Mamestra brassicac Panolis fiammea, Prodenia iitura, Spodoptera spp, Trichoplusia ni. Carpocapsa pomonclla, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana. From the order of the Coleoptera, e.g. B. Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus. Age

jastica alni. Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp .. Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp, Oryzaephilus surinamensis, Anthonomus spp, Sitophilus spp, Otiorrhynchus sulcatus. Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp, Trogoderma spp- Anthrenus spp, Attagenus spp, Lyctus spp, Meligethes aeneus. Ptinus spp, Niptus hololeu cus, Gibbium psylloides, Tribolium spp, Tenebrio moliior, Agriotes spp, Conoderus spp, Melolontha melolontha, Amphimallon solstitialis, Costalytra zealandica.

From the order of the Hymenoptera, for. B. Diprion spp, Haplocampa spp, Lasius spp, Monomorium pharaonis, Vespa spp.

From the order of the Diplera, for. B. Aedes spp. Anopheles spp, Culex spp, Drosophila melanogaster, Musca spp, Fannia spp, Calliphora erythrocephala. Lucilia spp, Crysomyia spp, Cuterebra spp, Gastrophilus spp, Hyppobosca spp, Stomoxys spp. Oestrus spp, Hypoderma spp, Tabanus spp, Tannia spp, Bibio hortulanus, Oscinella frit, Phorbia spp, Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae.Tipula paludosa.

From the order of the Siphonaptera z. 3. Xenopsylla cheopis, Ceratophyllus spp. M.

From the order of the Arachnida, e.g. B. Scorpio maurus, Latrodectus mactans.

From the order of the Acarina z. B. Acarus siro, Argas spp, Ornithodoros spp, Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora. Boophilus spp, Rhipicephalus spp, Amblyomma spp, Hyalomma spp. Ixodes spp, Psoroptes spp, Chorioptes spp, Sarcoptes spp, Tarsonemus spp, Bryobia praetiosa, Panonychus spp, Tetraychus spp.

The active ingredients can be converted into the customary formulations, such as solutions. Emulsions,

Wettable powders, suspensions, powders, dusts, foams, pastes, soluble powders, granulates. Aerosols. Sus-

pension emulsion concentrates, seed powder, active ingredient-impregnated natural and synthetic substances, ultra-fine encapsulation in polymeric substances and in coating materials for seeds, also in formulations with fuel charges, such as smoking cartridges, cans, spirals and the like, as well as ULV cold and warm mist formulations. These formulations are prepared in a known manner, / .. B. by mixing the active ingredients with Extenders, i.e. liquid solvents, liquefied gases under pressure and / or solid carriers, optionally with the use of surface-active agents, that is to say emulsifiers and / or Dispersants and / or foam-generating agents. In the case of using water as an extender kf> nen z. B. organic solvents can also be used as auxiliary solvents. As a liquid solvent The following are essentially possible: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics

ίο or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic Hydrocarbons such as CyclolVixan or paraffins, e.g. B. petroleum fractions, alcohols such as butanol or Glycol and ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water; with liquefied gaseous extenders or carriers are liquids that are meant, which at normal temperature and are gaseous under normal pressure, e.g. aerosol propellants such as halogenated hydrocarbons and Butane, propane, nitrogen and carbon dioxide; as a solid carrier; natural rock flour, such as kaolins, Clays, talc, chalk, quartz, attapulgite, monlmorillonite or diatomaceous earth and synthetic rock flour, such as finely divided silica, aluminum oxide and silicates; as solid carriers for granulates: broken ones and fractionated natural rocks such as calcite. Marble. Pumice, sepiolite, dolomite and synthetic Granules made from inorganic and organic flours and granules made from organic material such as sawdust, Coconut shells, corn on the cob and tobacco stalks; as emulsifying and / or foaming agents: nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, z. B. alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolysates; as Dispersant: e.g. B. lignin, sulphite liquor and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, Granular or latex-shaped polymers are used, such as gum arabic, polyvinyl alcohol, polyvinyl acetate.

Dyes such as inorganic pigments, e.g. B. iron oxide, titanium oxide, ferrocyan blue and organic Colorants such as alizarin, azo-metal phthalocyanine and trace nutrients such as salts of iron, manganese. Boron, copper, cobalt, molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95 percent by weight of active ingredient, preferably between 0.5 and 90%.

The active compounds according to the invention are used in the form of their commercially available formulations and / or the use forms prepared from these formulations.

The active ingredient content of the use forms prepared from the commercially available formulations can be in vary widely. The active ingredient concentration of the use forms can range from 0.0000001 to 100% by weight of active ingredient, preferably between 0.01 and 10% by weight. The application takes place in a customary manner adapted to the application forms. When used against hygiene and primary pests, the active ingredients are characterized by excellent properties Residual effect on wood and clay as well as good alkali stability on limed substrates.

The active compounds according to the invention are used in the veterinary sector in a known manner, such as by oral use in the form of, for example, tablets, capsules, potions, granules, by dermal Application in the form of, for example, immersion (dipping), spraying (spraying), pouring on (pour-on and spot-on) and powdering as well as by parcntcral application in the form of, for example, injection.

Example A.
Plulclla-Tesi

Solvent: 3 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce an appropriate preparation of active ingredient, 1 part by weight of active ingredient is mixed with the specified amount of solvent and the specified amount of emulsifier and dilute the concentrate with Water to the desired concentration.

Cabbage leaves (Brassica oleracea) are sprayed with the preparation of active compound and are populated with dew Cabbage moth caterpillars (Plutella maculipennis).

After the specified times, the destruction is determined in%. 100% means that all caterpillars were killed; 0% means that none of the caterpillars have been killed.

Active ingredients. Active ingredient concentrations, evaluation times and results are given in the table below 1 shows:

Table I (plant damaging insects)
Plutella test

Active ingredients Active ingredient kill rate

concentration in S

in% after 7 days

CO - NH- CO - NH- <f V-Cl 0.1
0.01

65
0

CO - NH- CO - NH- <f \ - Cl 0.01
0.001

100

100

CO - NH - CO - NH- <? \ - O

<f \ —CO —NH — CO — NH— <f \ - O— «fV — CN

CH,
/ VCO- NH- CO - NH- / ~ \ - O- / ~ \ - CN

CO-NH-CO-NH- <f \ - O- <f> -CN

f V-CO-NH-CO-NH- <f V-O- / V-CN

e> - CO— NH— CO — NH— <f V— O— <fV— CN

0.1 100 0.01 100 0.001 100 0.1 100 0.01 100 0.001 100 0.1 100 0.01 100 0.001 100 0.1 100 0.01 100 0.001 100 0.1 100 0.01 100 0.001 100 0.1 100 0.01 100 0.001 100

table 1 (continued)

Effectiveness

Active ingredient kill rate

concentration in%

in% after 7 days

¹⁰ / VCO-NH-CO-NH- / VO- / VCN

CO-NH-CO-NH

²⁵ <f V-CO-NH-CO-NH

CN

0_ / FROM

CN

CN

CO-NH-CO-NH

CO-NH-CO-NH- <r V-CO-NH-CO-NH

f V-CO- NH- CO- NH- f \ -0- / V-CN

0.1 100 0.01 100 0.001 100 0.1 100 0.01 100 0.001 IQQ 0.1 100 0.01 100 0.001 100 0.1 100 0.01 100 0.001 100 0.1 100 υ, οΐ 100 0.001 100 0.1 100 0.01 100 0.001 100 0.1 100 0.01 100 0.001 100

Example B. Test with parasitic fliers: larvae

Solvent: 35 parts by weight of ethylene polyglycol monomethyl ether Emulsifier: 35 parts by weight of nonylphenol polyglycol ether

To produce an appropriate preparation of the active substance, 30 weights of the substances in question are mixed active substance with the specified amount of solvent that contains the above-mentioned proportion of emulsifier and dilute the concentrate thus obtained with water to the desired concentration.

About 20 fly larvae (Lucillia cuprina) are placed in a test tube which contains about 2 cm- ¹ horse muscles. 0.5 ml of the active ingredient preparation is placed on this horse meat. After 24 hours, the degree of destruction is determined in%. 100% means that all , and 0% that no larvae have been killed.

Active ingredients, active ingredient concentrations and results are shown in Table 2 below:

Table 2 (parasitic fly larvae)

Active ingredient

Active ingredient concentration in ppm

Killing effect in% Lucüis cuprisa

20th

^CH > OO

Cl

1000 300 100

> 50

> 50

25th

Cl

C-NH-C-NH-T

1000

CN 300

100

30th

1000 300

100

100

> 50

100 0

30th

35

40

Example 1

45

CO - NH-CO - NH

O-7 V-CN

To 835 g (0.03 mol) of 3-chloro-4- (4-cyanophenoxy) aniline in 100 cc of toluene, a solution of 5.6 g (0.03 mol) dropwise at 50 ⁰ C 2-Chloro-benzoyl isocyanate in 20 ecm toluene. The batch is ^{stirred at 60 °} C. for 1 hour. After cooling, the precipitated product is filtered off with suction, washed first with toluene and then with petroleum ether. After drying, 10 g (78% of theory) of 4-cyano-2'-chloro-4 '- [N- (N'-2-chlorobenzoyl) -ureido] -diphenyläther with the melting point of 186 ⁰ C.

50

55

60

The compounds of the formula are analogous to Example 1

R ²

CO — NH — CO — NH- € \ - O-

synthesized, whereby the yields were not optimized.

-CN

example R'n No. 2 2.6-F 3 2-Cl 4th 2-CHj 5 2,6-Cl 6th 2,6-F 7th 2-Br 8th 2-Cl 9 2,6-F 10 2-Br 11th 2-CH ₃ 12th 2-Br 13th 2.6-F 14th 2-F 15th 2-Cl 16 2,6-F 17th 2-Br 18th 2-y 19th 2,6-Cl ZO 2-Cl

yield

(% of theory)

Melting point Q ° C) '

Cl

Cl

Cl

Br

Br

Br

Br

Br

Cl

C!

Cl

Cl

Br

Br

Br

Br

Br

Br

Br

Br

Br

Br

* Cl

* Cl

635

495

725

545

425

605

825

495

233 211 177 220 218 206 192 226 194 206 216 242 217 205 2 * 6 222 197 247 206

Some of the starting materials to be used can be produced as described below:

50 g (0.42 mol) of 4-hydroxybenzonitrile are dissolved in 300 ecm of dimethyl sulfoxide and a solution of 27 g of potassium hydroxide are added to 30 ecm of water. 150 ecm of distillate are drawn off under vacuum. In addition 72 g (03 mol) of 3-bromo-4-chloro-1-nhro-benzene are added and the batch is heated to 80 ° C. for 1 hour another hour at 100 ° C. After cooling, the product is treated with ice water with the addition of methanol like it and then sucked it off. Obtained after washing with water and recrystallization from ethanol 63 g of the pure compounds with a melting point of 115-116 ° C.

b)

151 g (0.475 mol) of the 2-bromo-4-nitro-4'-cyanodiphenyl ether obtained under a) are dissolved in 700 ecm of ethanol and, after the addition of 40 g of Raney nickel-iron and 10 g of sodium bicarbonate, hydrogenated at 20.degree. To At the end of the hydrogenation, the solid products are filtered off with suction and the filtrate is concentrated. The residue will recrystallized from benzene / ligroin and melts at 103-105 ° C. The yield is 86 g (63% of theory).

The following connections can be established in the same way:

\ ^ Cl

with a melting point of 118 ^° C

-CN

10

Br

Cl

with a melting point of 167 ° C Br

H ₂ N

CN

Br

with a melting point of 166 ° C 10

20th

25th

30th

40 45

50 55 bO 65

Claims (2)

Patent claims: 1. Substituted benzoyl ureidodiphenyl ethers of the general formula I. CO-NH-CO-NH in which R ^{1 stands} for halogen or Cr to Q-alkyl, R ² for chlorine. Bromine or hydrogen, R ^{3 stands} for bromine or hydrogen, and π stands for an integer from 1 to 3 2. Process for the preparation of the substituted benzoyl ureidodiphenyl ethers according to Claim 1, characterized in that characterized in that one in each case in a manner known per se a) Phenoxyanilines of the general formula R ²